Alkylphenols and derivatives thereof via phenol alkylation by cracked petroleum distillates

ABSTRACT

There are disclosed novel compositions of matter comprising monoalkylphenols prepared by selectively alkylating the olefin component of a thermally cracked sulfur-containing petroleum distillate derived from residua. The monoalkylphenols have certain ortho to para ratios and may be used to prepare a number of useful derivatives such as ethoxylated and propoxylated surfactants, sulfoalkylated products, sulfurized antioxidants, overbased phenates, dithiophosphate derivatives, formaldehyde reaction products and similar methylene bridged products which are useful demulsifiers.

This is a continuation of application Ser. No. 113,619 filed 10/26/87,now U.S. Pat. No. 4,914,246, which is a CIP of U.S. Ser. No. 922,87710/24/86, abandoned.

FIELD OF THE INVENTION

This invention relates to novel compositions of matter and methods ofmaking the same. More particularly, this invention relates to thealkylation of phenols by olefinic components of cracked petroleumdistillates to produce novel alkylphenols; and to derivatives of thealkylphenols.

As such the invention is related to the composition, separation andalkylation chemistry of olefinic cracked petroleum distillatesespecially of thermally cracked petroleum residua of high sulfurcontent.

The invention is particularly related to the chemistry of C₈ and higheralkylphenols. It is aimed at the preparation of semilinear alkylphenolsderived by alkylating phenols with the largely linear olefin componentsof distillates derived by the high temperature thermal cracking ofpetroleum residua. Furthermore, the invention is concerned with theethoxylation and propoxylation of alkylphenols, particularly of thosederived from cracked petroleum distillates, especially cokerdistillates. The preparation of sulfate and sulfonate derivatives of theethoxylated and propoxylated alkylphenol products is also described.Finally, the conversion of alkyl phenols to sulfurized metal phenateoverbased detergents is discussed.

PRIOR ART VERSUS THE PRESENT INVENTION

The alkylation of phenols by olefins in the presence of acids to producealkylphenols is a well known reaction. Indeed, alkylphenols are used ina wide variety of applications. For example, ortho alkylphenols aresuperior antioxidants compared to para alkylphenols as described in U.S.Pat. No. 3,929,654. The C₈ and higher branched alkylphenols arecommercially used for the production of ethoxylated nonionic surfactantsand their anionic sulfate and sulfonate derivatives. In this regard, see"Nonionic Surfactants" M. J. Schick, editor, M. Dekker, Inc., New York,NY, 1966, especially pages 44 to 85. For the chemistry of sulfate andsulfonate derivatives of alkylphenols, see also "Sulfonation Reactions",E. E. Gilbert, Interscience Publishers, New York, NY, 1965, particularlypages 378, 379, 350 and 297. The sulfation and sulfonation ofethoxylated alkylphenols is also described in U.S. Pat. Nos. 2,143,759;2,106,716; 2,184,935; and 3,150,161. Other uses of alkylphenolderivatives include automotive lubricants additives. See, for example,"Lubricants and Related Products", D. Klamann, Verlag Chemie, Weinheim,W. Germany, 1984, particularly pages 181, 182, and 199.

As indicated above, alkylphenols are used in the preparation ofsurfactants. The most frequently used alkylphenol surfactantintermediates are t-octylphenol, t-nonylphenol and t-dodecylphenol. Theyare commonly prepared by the alkylation of phenol of diisobutylene,propylene trimer and propylene tetramer, respectively. These are highlybranched alkylphenols, generally 95% being para substituted.

In contrast to the highly branched alkylphenols, there are knownso-called linear alkylphenols. When produced via low temperaturealkylation at about 80° C., these alkylphenols generally consist ofclose to a statistical mixture of ortho and para isomers, i.e., 66 to33. These intermediates are prepared using linear alpha olefins asalkylating agents. Thus, U.S. Pat. No. 3,423,474 and Soviet Patent No.882,995 disclose alkylations of phenols with alpha olefins as reactants.U.S. Pat. Nos. 3,312,734 and 3,432,567 disclose similar alkylations withcracked wax olefins. Also, U.S. Pat. No. 3,630,918 discloses thepreparation of metal dialkyl dithiophosphate derivatives fromalkylphenols derived from cracked wax olefins.

In U.S. Pat. No. 3,639,490 the alkylation of phenol or cresols by theolefinic components of a C₆ to C₈ catalytic gasoline stream to producebranched chain alkylphenol antioxidants is disclosed.

None of the foregoing references, however, teach the preparation ofsemilinear alkylphenols, i.e. alkylphenols derived from olefinscomprising of major quantities of linear and minor quantities ofbranched olefins. There was no known olefinic feed for the preparationof such products.

As a part of the present invention it was discovered that thermallycracked petroleum distillates, particularly those derived from residualfuel oil by Fluid-coking and Flexicoking, contain unexpectedly majorquantities of linear olefins and minor quantities of branched olefins.These olefins are valued below distillate fuel cost, because suchcracked distillates have high concentrations of sulfur compounds andhave to be extensively hydrogenated before they can be used asdistillate fuels. The olefin components are converted to paraffinsduring such hydrogenations.

Furthermore, it was found in the present invention, that the sulfurcompounds in such thermally cracked petroleum distillates are mostlyinert aromatic, thiophene type compounds rather than catalyst inhibitingmercaptans.

A group preferred thermally cracked distillates, not previouslyconsidered as an alkylation feed, comprises naphtha and gas oilfractions produced in fluidized coking units. Integrated fluidizedcoking processes such as Fluid-coking and Flexicoking represent asuperior refinery method for the conversion of residual fuel oil. Thethermal cracking step of Fluid-coking and Flexicoking is identical.However, Fluid-coking does not utilize the residual coke produced withthe coker distillate while Flexicoking employs the coke by-product forthe production of low thermal value gas. A discussion of these processesis found in U.S. Pat. Nos. 2,813,916; 2,905,629; 2,905,733; 3,661,543;3,816,084; 4,055,484 and 4,497,705 which are incorporated as references.

The preferred Fluid-coking and Flexicoking processes are low severitythermal cracking operations. Low severity is usually achieved by keepingthe temperature relatively low in the range of 482° to 538° C. (900° to1000° F.) while using a long residence, i.e., contact, time of about 20to 60 seconds. Alternately, low severity can be achieved by using hightemperatures, in the order of 538° to 705° C. (1000° to 1300° F.) andcontact times of less than 5 seconds. In a long residence timeoperation, additional amounts of the desired olefin components can beproduced by reinjecting the heavy gas oil distillate products into thecracking line.

The residual fuel feeds for the above coking processes are usuallyvacuum residua which remain after most of the crude petroleum is removedby refinery distillation processes. As such these residua typicallypossess boiling points above 565° C. (1050° F.) and have Conradsoncarbon contents above 15%. These residua contain most of the undesirablecomponents of the crude, i.e. sulfur and nitrogen compounds and metalcomplexes. On coking much of the sulfur ends up in the distillateproducts. As a result of high temperature thermal cracking, majoramounts of olefinic components are also formed and become majorconstituents of such distillates. In spite of their high monoolefincontent such distillates generally were not considered as alkylationfeeds because of their high sulfur and conjugated diolefin content. Itwas surprisingly found in the present invention that, in spite of thehigh sulfur content, the olefinic components of such feeds selectivelyreact with added phenol to form semilinear alkylphenols.

The semilinear alkylphenols of the present invention differ from thehighly branched and linear alkylphenols of the prior art in both thebranchiness and the ortho versus para isomer distribution. They containfrom about 1.4 to 2 branches per alkyl substituent on the average andortho to para alkyl substituent ratios ranging from about 10/90 to40/60.

DESCRIPTION OF THE FIGURES

FIG. 1 shows the capillary gas chromatogram of a Fluid-coker naphthafeed in the C₄ to C₁₂ range, with an indication of the major 1-n-olefinand n-paraffin components.

FIG. 2 shows the 400 MHz proton nuclear magnetic resonance spectrum ofthe olefinic protons of Fluid-coker naphtha feed, with an indication ofthe chemical shift regions of various types of olefins.

FIG. 3 shows the capillary gas chromatogram of the light Fluid-coker gasoil feed in the C₉ -C₁₅ range, with an indication of the major1-n-olefin and paraffin components.

FIG. 4 shows the capillary gas chromatogram on a highly polar column ofa C₁₂ fraction of light Fluid-coker gas oil, with separation of varioustypes of aliphatic and aromatic components and sulfur compounds.

FIG. 5 shows the separation of a 1-n-olefin - n-paraffin mixture from aC₁₆ -C₁₉ Fluid-coker gas oil fraction by crystallization.

FIG. 6 shows the ¹³ C NMR spectrum of a highly branched dodecylphenolproduct of the prior art at the top and the spectrum of a comparativelysemilinear dodecylphenol of the present invention at the bottom.

SUMMARY OF THE INVENTION

In its simplest sense, the present invention is predicated on thediscovery that phenols can be selectively alkylated with the olefincomponent of a thermally cracked sulfur containing petroleum distillatederived from residua in the presence of an acid catalyst to providemonoalkylphenols which have an average of less than two alkyl branchesin the said alkyl group. The monoalkylphenols so obtained generallypossess ortho to para ratios of about 10 ortho to about 90 para isomersto about 40 ortho to about 60 para isomers. Various derivatives of suchalkylphenols are also contemplated.

Broadly stated then, the present invention is directed toward novelcompositions of the following formula: ##STR1## wherein

R is a C₁ to C₃₅, preferably C₅ to C₃₅, more preferably C₈ to C₂₉, mostpreferably C₉ to C₂₀ alkyl, C₉ and C₁₂ alkyl groups being specificallypreferred; R is in an ortho and/or para position relative to thephenolic OZ group, with the proviso that at least one R is a higher C₅to C₃₅ alkyl group said alkyl groups having an average of less than twobut more than one branches therein, p is 1 or 2, preferably 1 with theproviso that if p is 1, the ratio of o- to p- R groups is from about 10to 90 to about 40 to 60; preferably from about 20 to 80 to about 30 to70;

Z is a phenolic hydrogen or a substituent member of the group consistingof Na, K, Ca, Mg, (EO)_(n) H, (EO)_(n) (CH₂)₂ SO₃ M (EO)_(n) (CH₂)₃ SO₃M and (EO)_(n) CH(CH₃)CH₂ CH₂ SO₃ M wherein E is CH₂ CH₂, CH₂ CH(CH₃),CH(CH₃)CH₂ ; M is H, Na, K, ammonium, Ca, Mg and n is 1 to 30;preferably 1 to 15;

Q is a bridging radical selected from the group consisting of S, S₂ andCH₂ with the proviso that if Q is S or S₂, Z is H, Ca or Mg and if Q isCH₂, Z is (EO)_(m) H; q, the number of bridging groups, is 0 to 15 withproviso that if Q is S or S₂, q is in the range of 1 to 5; m, the numberof phenolic groups is 1 to 16, m being 1+q;

Y is selected from the group consisting of H and SO₃ M in which it isdefined as above with the proviso that if Y is SO₃ M, q is preferably 0and Z is (EO)_(n) H;

The semilinear alkylphenol intermediates of the present invention areprepared according to the present process by reacting phenols with theolefin components of the high temperature cracking of sulfur containingresidua, and are of the formula ##STR2## wherein the meaning of R and pis as defined before. M is H or Na, K, Ca, Mg, Co, Ni. Specifically,preferred semilinear alkylphenols are octylphenol, nonylphenol,undecylphenol, dodecylphenol. The preferred semilinear monoalkylphenolcompositions possess o- to p- ratios of their alkyl groups in the rangeof about 10 to 90 to about 40 to 60.

In the preferred monophenol compositions, the value of Q is 0. In thiscase, the compounds generically are of the formula ##STR3## wherein OZrepresents a phenolic group in which Z is selected from the groupconsisting of H, Na, K, Ca, Mg, (EO)_(n) H and (EO)_(n) (T).sub.(t)(SO₃)_(u) and in which E is selected from the group consisting of CH₂CH₂, CH(CH₃)CH₂ and CH₂ CH(CH₃), n is 1 to 30, T is selected from thegroup consisting of CH₂ CH₂, CH₂ CH₂ CH₂, CH(CH₃)CH₂ CH₂, t is 0 or 1, mis H, Na, K, ammonium, Ca, mg, Ni, Co, or Fe, and u is 0 or 1 providedthat if t is 1, u also is 1; and Y is selected from the group consistingof H and (SO₃)M in which M is as defined above; and R is selected fromthe group consisting of C₅ to C₃₅ branched alkyl groups having anaverage of about 1.4 to about 2 branches therein in an ortho and/or pararelationship to the phenolic OZ group and in which p is 1 or 2 providedthat when p is 1, the ratio of ortho to para isomers is between about 10ortho to about 90 para to about 40 ortho to 60 para isomers, preferablyfrom about 20 to 80 to about 30 to 70.

The present invention also is directed toward a method of preparingthese compositions.

These and other features of the invention will become more readilyunderstood upon a reading of the detailed description of the inventionwhich follows.

DETAILED DESCRIPTION OF THE INVENTION

The alkylphenols of the present invention are prepared by reactingphenol with a hydrocarbon feed containing more than 15% monoolefinshaving C₅ to C₃₅ carbon ranges. These monoolefins contain from about 30to 50% 1-n-olefin, 15 to 30% linear internal olefin and 30 to 45%monobranched olefins and have terminal to internal unsaturation ratiosbeing in the range of from about 1.5 to 1 to about 4 to 1. Indeed, it ispreferred that the hydrocarbon feed employed in the practice of thepresent invention be an olefin containing distillate fraction ofthermally cracked hydrocarbons derived from petroleum residua.Consequently, specific mention is made hereinafter to olefin containingdistillate fractions of thermally cracked residua; however, it will beappreciated that other feeds having substantially similar properties canbe employed.

The preferred cracked distillates of the present feed contain relativelyhigh amounts of organic sulfur compounds. The sulfur concentrations arepreferably between 0.1% (1000 ppm) and 5% (50,000 ppm) more preferablybetween 0.5% (5000 ppm) and 4% (40,000 ppm). The prevalent sulfurcompounds of the preferred feeds are aromatic, mainly thiophenic. Mostpreferably the aromatic sulfur compounds represent more than 90% of thetotal. In view of this characteristic of the feed, the present findingof selective phenol alkylation is surprising since thiophenes are highlyreactive and tend to polymerize under acid conditions.

To summarize, the olefin-containing reactant used as a feed in thepresent invention will generally have from C₅ to C₃₅ carbon ranges. Morepreferably, the carbon range in such olefin-containing fractions will befrom C₈ to C₂₉ and most preferably from C₉ to C₂₀. Additionally, it isparticularly preferred in the practice of the present invention thatgreater than 25%, for example, 30% to 80% of the olefins in the feed belinear aliphatic olefins.

As indicated, the olefin feed is reacted with phenol. Normally at leastone mole of phenol per mole of olefin will be employed; however, it isgenerally preferred to use excess phenol.

The reaction of phenol and the olefinic feed is conducted attemperatures sufficient to alkylate the phenol. In general these aretemperatures of about 20° C. and 450° C. and preferably from about 20°C. to 50° C. more preferably from 80° to 130° C.

Importantly, the reaction is conducted in the presence of an effectiveamount of an acid catalyst. In general, the acid concentration in thereaction mixture will vary from about 1% to about 50% by weight andpreferably from 5% to 25%.

Among the acid catalysts that are suitable in the practice of thepresent invention are strong acids such as sulfuric acid, phosphoricacid, phosphonic acid, sulphonic acid, inorganic polyacids, such asaluminosilicate clays, acidic cation exchange resins, such as sulfonicacids, based on crosslinked styrene, divinylbenzene polymers, borontrifluoride, hydrogen fluoride, tetrafluoroboric acid and other combinedacids. Insoluble acid catalysts are preferred. The particularlypreferred catalyst in the process of the present invention is a sulfonicacid derivative of an insoluble cross-linked styrene, divinyl resin.

It should be readily appreciated that reaction of phenols with linearolefins will lead to alkylphenol products which can be further alkylatedto provide dialkylphenols. Formation of such dialkyl phenols can besuppressed, if desired, by employing a large excess of phenol reactantand employing relatively mild reaction conditions.

Also, as will be readily appreciated, the alkylphenol reaction productsof the present process can be separated from unreacted feed componentsby standard separation techniques such as fractional distillation.

Another aspect of the present invention is the conversion of thealkylphenol products derived from cracked distillates. The mostimportant type of conversion provides novel surfactants, preferably viaethoxylation and/or propoxylation. In another important reaction, suchalkylphenols or their ethoxylated/propoxylated derivatives are reactedwith propanesultone, butanesultone or sulfuric acid to produce sulfonatesurfactants. In a different reaction, semilinear alkylphenols areconverted to overbased automotive lubricant additives, preferably byreaction with sulfur and calcium oxide plus carbon dioxide. Furthermore,semilinear alkylphenols can be also employed to prepare demulsifieradditives by reacting them with formaldehyde and ethylene oxide. Thereaction of the present alkylphenols with sulfur dichloride provides anantioxidant for automotive lubricants. Metal derivatives of suchcompounds act as octane number improvers as disclosed in U.S. Pat. No.4,536,192 by Braid et al. (assigned to Mobil Oil Corp.). Via anotherreaction with phosphorus pentasulfide, zinc dialkylaryl dithiophosphatelubricant additives are produced.

The processes converting the semi-linear alkylphenol intermediates ofthe present invention to useful products are carried out under prior artconditions, developed for highly branched alkylphenols. However, thesefurther conversions of the present alkylphenols as a part of amulti-step process have a further advantage. In general, they producehigher boiling, less volatile products which can then be betterseparated from the unreacted cracked distillate components andalkylation by-products than the alkylphenol intermediates. The productimpurities can be simply removed by distillation in vacuo.

Olefinic Thermally Cracked Feeds

The olefinic feed of the present process is a critical factor inproducing the novel alkylphenols at a low cost. The preferred feed isproduced by thermal cracking of petroleum residua.

Thermal cracking of petroleum residua produces hydrocarbons of morelinear olefinic character than catalytic cracking does. It was found inthe present invention that the percentage of olefins including1-n-olefin components in thermally cracked petroleum distillatesgenerally increases with increases in the cracking temperature.Therefore, the olefin containing distillate fractions derived frompetroleum residua by high temperature thermal cracking processes arepreferred feeds for alkylation of phenols in accordance with the presentinvention of the present process.

There are two main commercial processes for producing thermally crackedpetroleum distillates from residua. They were reviewed by Jens Weitkampin the journal, entitled Chem. Ing. Tech. No. 2, pages 101-107 in 1982.These processes are coking visbreaking, representing severe and mildcracking processes. The main coking processes are Flexicoking andFluid-coking which produce the preferred distillate feeds of the presentinvention.

Suitable distillate feeds can be also prepared in thermal processesemploying a plurality of cracking zones at different temperatures. Sucha process is described in U.S. Pat. Nos. 4,477,334 and 4,487,686. Eachof these thermal cracking processes can be adjusted to increase theolefin content of their products. Heavy gas oil distillates can befurther cracked to increase the amount of lower molecular weightolefins.

The olefin containing distillate fractions of thermal cracking processesmay be employed as feeds in the process of the invention without priorpurification; however, these distillate fractions may optionally betreated prior to their use to reduce concentrations of aromatichydrocarbons, sulfur and nitrogen compounds if so desired. For example,aromatic hydrocarbons and sulfur compounds can be selectively extractedfrom the olefin containing fraction by polar solvents. Mercaptancomponents can be removed with base. Nitrogen and sulfur compounds ingeneral can be removed by use of absorption columns packed with polarsolids such as silica, Fuller's earth, bauxite and the like. In thehigher fractions, more than 90% of the sulfur compounds are present asthiophenic compounds, i.e., alkylthiophenes, benzothiophenes, etc. Hightemperature fixed beds of either bauxite or Fuller's earth or clay canbe used to convert sulfur compounds to easily removable H₂ S with aconcurrent isomerization of the olefin components.

The conjugated olefin components of the present feeds may be removed byprior mild hydrogenation or selective alkylation prior to use. Thebranched olefin components can be similarly removed e.g. by water,alcohol or acid addition. 1-n-Olefin components can be selectivelyreacted via hydroformylation or removed together with the n-paraffins bycocrystallization.

The cracked refinery distillate products, light and heavy naphthas andgas oils, are preferably further fractionated prior to use in thepresent process. The preferred broad carbon ranges of the thermallycracked feeds are from C₅ to C₃₅. A more preferred carbon range is fromC₈ to C₂₉. The most preferred range is from C₉ to C₂₀. It is desirableto limit the carbon number range of any given distillate feed byefficient fractional distillation to five carbons, preferably threecarbons and more preferably to one carbon to facilitate the separationof alkylphenol products of increased boiling range from the unreactedfeedstock.

Specifically, preferred feeds are C₉ and C₁₂ cracked distillatefractions for the preparation of semilinear C₉ and C₁₂ alkylphenols,respectively. In case of very sharp distillate fractions within a singlecarbon range, the ratio of the different types of isomeric olefincomponents depends on the boiling range point.

The olefin content of the present cracked distillate feeds is about 15%,preferably above 30%, more preferably above 40%. The 1-n-olefins arepreferably the major type components.

The main olefin reactant components of the present feeds are nonbranchedTypes I and II plus mono-branched Types III and IV as indicated by thefollowing formulas (R=hydrocarbyl, preferably non-branched alkyl):##STR4##

The concentration Type I olefins is preferably from about 30 to 50% ofthe total olefin concentration. Similarly, the percentage of Type IIolefins preferably from about 15 to 30%. Type V olefins of formula R₂C═CR₂ are essentially absent.

The n-alkyl substituted Type I olefins, i.e. 1-n-olefins, are generallypresent in the highest concentration in these thermally crackeddistillate feeds.

Alkylation Process of the Invention

The alkylation process of the present invention comprises reacting anolefinic cracked petroleum distillate feed, preferably produced frompetroleum residua by high temperature thermal cracking and containing1-n-olefins as the major type of olefin components and organic sulfurcompounds, between 0.1 and 5% sulfur, more preferably between 0.5 and4%,

with phenol or cresol, preferably phenol, employing at least one mole ofexcess phenol per mole olefinic reactant, preferably in the liquidphase, at least one mole of excess phenol per mole olefinic reactant,preferably in the liquid phase, at temperatures between about 20° and450° C., preferably from 20° to 150° C., more preferably from 80° to130° C., in the presence of effective amounts of an acid catalyst,preferably a strong acid insoluble in the reaction medium,

to produce alkylphenols as the major products, preferably a C₈ to C₃₀semilinear monoalkylphenol and preferably including, in addition to saidalkylation process step, the step of reacting the alkylphenol

(a) either with an alkoxylating agent selected from the group consistingof ethylene oxide and/or propylene oxide to produce an ethoxylatedand/or propoxylated alkylphenol nonionic surfactant and preferentiallyconverting the said nonionic surfactant to a sulfonate surfactantderivative preferably by reacting it with propanesultone orbutanesultone

(b) or with a sulfoalkylating agent, preferably selected from the groupconsisting of propanesultone and butanesultone, to produce analkylphenoxyalkanesulfonate surfactant

(c) or with sulfur dichloride to produce a sulfurized alkylphenololigomer antioxidant, largely o,o'-bis-alkylphenyl sulfide,preferentially converting said antioxidant to an overbased metal phenatedetergent by reacting it with calcium hydroxide or magnesium hydroxidein the presence of CO₂.

(d) or with phosphorus pentasulfide to produce a di-alkylaryldithiophosphate additive by reaction with zinc oxide

(e) or with formaldehyde to produce an o,o'-bis-alkylphenyl methanedimer and other methylene bridged, oligomeric polyphenols and convertingsaid polyphenols to their ethoxylated and/or propoxylated demulsifierderivatives by alkoxylation reactions with ethylene oxide and propyleneoxide, respectively.

In the selective phenol alkylation process of the present invention thebranched olefin components of the feed react at a faster rate than thelinear olefins due to the better stabilization of the tertiary cationintermediates; e.g. in the case of p-alkylphenols: ##STR5## In the caseof the less reactive linear olefins, isomerization is a common sidereaction, particularly at low temperature. Thus, 1-n-olefins provide notonly methyl but higher alkyl branched alkylphenols dependent on thereaction conditions, e.g. ##STR6##

In general, branched olefins lead to t-alkylphenols while linear olefinsprovide s-alkylphenols. Thus the ratio of tertiary versus secondaryalkylphenol products depends on the ratio of branched versus linearolefins reacted. The prior art isoalkylphenols derived from branchedolefins are essentially all t-alkylphenols.

Branched olefins provide mostly para tertiary alkylphenols while linearolefins lead to mixtures of ortho and para secondary alkylphenols.1-n-Olefins can give an o/p isomer mixture close to statistical i.e. a66 to 33 o/p ratio. Thus the present process provides products ofincreasing o/p ratios with increasing olefin conversion of the crackeddistillate feeds.

The monoalkylphenol products of the present process can be furtheralkylated to provide 2,4-dialkylphenols. For example, 1-n-olefins yieldsome of the following compounds: ##STR7##

The formation of such dialkylphenols can be suppressed by employing alarge excess of the phenol reactant and relatively mild reactionconditions.

One of the preferred catalysts of the present process is the sulfonicacid derivative of an insoluble crosslinked styrene divinylbenzeneresin. This catalyst is preferably employed at temperatures below 150°C. to avoid decomposition and the formation of soluble sulfonic acids.Insoluble solid acids can be simply removed from the reaction mixture byfiltration.

The alkylphenol products of the present process can be separated fromthe unreacted feed components by fractional distillation. However, it isimportant the all strong acids be removed or neutralized prior todistillation because at high temperature they can lead to a catalyticreversal of the alkylation reaction.

The alkylphenol products of the present invention, particularly thesemilinear monoalkylphenols, can be derivatized to provide severaldifferent types of useful compositions. The monoalkylphenolintermediates can be further converted either prior to or afterseparation. Derivatization of the crude monoalkylphenol reactionproducts is often advantageous from the separations point of view sincethe derivatives are less volatile.

Alkoxylation

The alkylphenols can be ethoxylated and/or propoxylated in the presenceof acid or base catalysts to provide alkylphenyl polyoxyethyl and/orpolyoxypropyl alcohols. The first step of such base catalyzedalkoxylation reactions is much faster than those of the subsequentsteps, e.g., in case of the p-alkylphenols. ##STR8## After thealkylphenol is monoethoxylated or propoxylated the high boiling productscan be readily separated from the much lower boiling impurities bydistillation.

The monoalkoxylated product can then be further reacted, e.g.ethoxylated or propoxylated. The acid catalyzed propoxylation is furtherdiscussed in the following because it forms mixtures of primary andsecondary propoxylated alcohols; e.g. ##STR9## Thus, in an attractiveprocess variant the alkylphenoxyethanol or alkylphenoxypropanolmonoalkoxylation product is isolated by distillation and then furtherderivatized. Further ethoxylation of alkylphenoxyethanol results in aPoisson distribution of variously ethoxylated alkylphenol products. Asimilar behavior is observed in the propoxylation ofalkylphenoxy-2-propanol. However, in case of propoxylation the isomericproduct composition depends on the presence of base versus acidcatalyst.

In general, the base catalyzed ethoxylation and propoxylation of thepresent alkylphenols is preferred because of the high rate andselectivity of monoalkyoxylated product formation. Acids are poorcatalysts of phenol-epoxide reactions. Selective formation of themonoalkoxylated products is particularly advantageous when the startingcracked olefin derived alkylphenol reactants are of a fairly broadboiling range and contain hydrocarbon and sulfur compounds asimpurities.

While propoxylation in the presence of base catalysts essentially formsonly secondary alcohols, in the presence of acid catalysts the majorproduct isomer is the primary alcohol, e.g.2-alkylphenoxyethoxylpropanol-1. On further propoxylation in thepresence of acid catalysts, the addition of primary and secondarypropanol units continues. The generic formula of the resultingethoxylated propoxylated alcohols is indicated in the following reactionscheme: ##STR10## wherein Pr is CH(CH₃)CH₂ or CH₂ CH(CH₃). Theseproducts contain propylene moieties of different orientation and possessmainly alcohol end groups.

As base catalysts of alkoxylation sodium hydroxide and potassiumhydroxide are frequently used. These catalysts react with alkylphenolsto form the corresponding alkali phenolate. The latter in turn furtherreacts with the ethylene oxide or propylene oxide to produce a growingalkoxide moiety. Instead of alkali hydroxides, sodium or potassium mayserve as precursors of the phenolate or alcoholate species. Themolecular weight of the alkoxylated product is controlled by the phenolto ethylene oxide and/or propylene oxide ratio.

As acid catalysts of alkoxylation p-toluenesulfonic acid, silicontetrafluoride, crosslinked polymeric sulfonic acids, antimonypentachloride, tin tetrachloride, trifluoromethanesulfonic acid andother strong acids can be used. Combinations of BF₃ with metal alkyls orhydrides e.g. of Al, Ti can be also employed. To avoid thepolymerization of ethylene oxide, and/or propylene oxide, anhydroussystems are preferred.

Sulfation and Sulfonation

Cracked olefin derived alkylphenols and their ethoxylated/propoxylatedderivatives both react readily with sulfuric acid and sulfur trioxide toform sulfates and sulfonates. Other sulfonating agents are complexes ofSO₃ and sodium hydrogen sulfite. The latter is employed either in theStrecker reaction of halides and sulfates or addition reactions witholefinic derivatives. The ethoxylated alkylphenols are first sulfatedunder mild conditions and then sulfonated. Acid hydrolysis of theresulting sulfate sulfonate leads to the sulfonate as indicated by thefollowing reaction scheme: ##STR11## wherein the meaning of the symbolsR and n is the same as before. Metal and ammonium slats of thesesulfates and/or sulfonates are useful surfactants.

Sulfonate derivatives can be also prepared by reacting the alkylphenolsand their ethoxylated/propoxylated derivatives with a sulfoalkylatingagent. For example, the reaction of alkali metal derivatives withpropanesultone on butanesultone lead to the corresponding sulfonatesalts ##STR12## Other sulfoalkylating reagents are bromoethanesulfonateand vinylsulfonate salts.

Condensation with Sulfur Chlorides

Alkylphenols can be sulfurized primarily by technical sulfur dichloride,a mixture of SCl₂ and S₂ Cl₂, preferably at about 80° C. to providesulfur bridged condensation products having about 3 phenol moieties permolecule. For example, in the case of a nonylphenol dinonyphenol mixturethe following product is formed: ##STR13## After the removal by thepurging of all the HCl by-product and unreacted components from thereaction mixture, the product can be used as an antioxidant component ofcrankcase oil, an automotive lubricant. Similar products can also beused as additive intermediates.

As a preferred example, sulfurized 4-t-dodecylphenol is used for thepreparation of an overbased detergent additive based onmonoalkylphenols. Dodecylphenol is largely converted to thecorresponding overbased calcium dodecylphenolate by reacting it in ahigher alcohol solvent with elemental sulfur and calcium oxide in thepresence of ethylene glycol and then carbon dioxide. Although the exactsequence of reactions is not known, the main course of the reaction canbe indicated by the following scheme. ##STR14##

The viscosity of the i-dodecylphenol intermediate of the above schemedepends on the branchiness of the i-dodecyl group. A reduced viscosityis desired for the ease of processing. The reduced branchiness of thedodecyl group of the cracked olefin derived alkylphenol resulted inadvantageously reduced viscosity and thus improved processability.

The overbased calcium dodecylphenolate product is used as a detergentadditive component of marine engine oils and crankcase oils. As anadditive it is acting not only as a detergent antioxidant but as aneutralizer of acidic oxidation by-products.

Overbased magnesium alkylphenolates can be also prepared and are usefulas superior detergent additives. However, in their synthesis the keymagnesium hydroxide reactant is to be derived from a magnesiumalcoholate. For example, in the case of the overbased magnesiumdodecylphenolate, the overall process scheme is the following: ##STR15##

Condensation with Formaldehyde

Alkylphenols derived from cracked distillates are readily condensed withformaldehyde. The resulting methylene bridged condensation products arethen ethoxylated and/or propoxylated, preferably in the presence of abase catalyst, to provide oligomeric surfactants useful as demulsifiers,fuel additives and coal slurry stabilizers. The reaction scheme isillustrated with nonylphenol in the following: ##STR16## wherein m is 0to 15, preferably 1 to 10, n is 1 to 30.

Reaction with Phosphorus Pentasulfide

Semilinear alkylphenols of the present invention are readily reactedwith phosphorus pentasulfide via known methods. For example, the methoddescribed by Bencze in the journal "Schmierstoffe undSchmierungstechnik," No. 5, pages 4 to 16 in 1966, may be used. Theresulting bis-alkylaryl dithiophosphoric acids are in turn converted tothe corresponding zinc dialkyldithiophosphates as indicated by thefollowing reaction scheme: ##STR17## The zinc dialkyldithiophosphateproducts, which usually contain excess Zn as hydroxide, are hightemperature antioxidants useful as lubricating additives.

Alkylphenol Derived Compositions

The ethoxylated and/or propoxylated semilinear alkylphenol compositionsare also derived by alkylating phenols with the olefin components ofthermally cracked distillates in the first step. They are of the formula##STR18## wherein the meanings of R and p are as previously defined; Eis CH₂ CH₂, CH(CH₃)CH₂ and CH₂ CH(CHCH₃, preferably CH₂ CH₂, n is 1 to30, more preferably 1 to 15. Monoethoxylated compositions where n is 1are specifically preferred: ##STR19##

The most important derivatives of the present ethoxylated and/orpropoxylated alkyl phenols are the sulfates and sulfonates. They arepreferably of the formula ##STR20## wherein the meaning of R, p, EO andn is the same as previously defined;

T is CH₂ CH₂, CH₂ CH₂ CH₂, CH(CH₃) CH₂ CH₂, preferably CH(CH₃)CH₂ CH₂ ;t is 0 or 1; M is H, Na, K, Ca, Mg, Ni, Co, Fe, preferably H and Na; uis 0 or 1 with the proviso that if t is 1, u must be also 1, and r is 0or 1.

A preferred subgenus of the above compounds consists of sulfatederivatives of ethoxylated alkyphenols of the formula is a precursor ofthe ethoxylated sulfonate of the formula ##STR21## The sulfate sulfonateof the above formula is a precursor of the ethoxylated sulfonate of theformula ##STR22## wherein the meaning of the symbols is the same.

Another preferred type of sulfonate derivative of the presentethoxylated monoalkylphenol is of the formula ##STR23## wherein thegeneric meaning of the symbols, R and T is the same. n is 1 to 35preferably 1 to 15. A specific preferred group of sulfonates of thistype is ##STR24## The mono ethoxylated sodium sulfonate compound isspecifically preferred: ##STR25##

Another type of composition derived from the present semilinearalkylphenols comprises sulfur bridged antioxidant compounds of theformula ##STR26## wherein the meaning of R and p is the same, R is morepreferably C₈ to C₁₂, most preferably C₉ alkyl, the bridging sulfurgroups are in ortho para positions relative to the phenolic hydroxyl,mostly ortho, x is 1 or 2, mainly one and v is 0 to 6, preferably 1 to3. The sulfur bridged semilinear nonylphenol, having an average value ofv between 0 and 2, preferably equaling 1, is specifically preferred.

Sulfur bridged overbased calcium and magnesium phenate derivatives ofsemilinear monoalkylphenols are detergent additives of a distinct type.They contain structural units of the formula ##STR27## wherein themeaning of R is a C₅ to C₃₅ alkyl, preferably, a C₉ to C₁₈ alkyl, mostpreferably C₁₂ alkyl; M is Ca or Mg, preferably Ca.

Methylene bridged semilinear mono alkylphenols and their ethoxylatedand/or propoxylated derivatives represent another subgenus of thepresent compositions. They are of the formula ##STR28## wherein themeaning of R is a C₅ to C₃₅ alkyl, preferably a C₈ to C₁₅ alkyl, mostpreferably a C₉ alkyl, in an ortho and/or para position relative to thephenolic group. The bridging methylene groups are in an ortho or para,mostly ortho, position relative to the phenolic group, p is 1 or 2,preferably 1, m is 0 to 15, preferably 1 to 10, E is CH₂ CH₂, CH₂CH(CH₃)CH₂ preferably CH₂ CH₂, n is 0 to 30, preferably either 0 to 30.

Bis-alkylaryl dithiophosphate antioxidant additive derivatives of thepresent semilinear monoalkylphenols form another subgenus of the formula##STR29## wherein R is C₅ to C₃₅ preferably C₈ to C₁₂ alkyl, in an orthoand/or para position relative to the phenolic oxygen, M is H,(Zn)_(1/2), ZnOH, preferably Zn_(1/2).

EXAMPLES

In the following, examples are provided to illustrate the presentprocess of phenol alkylation and its products, without limitinginvention. As an introduction to the examples the cracked distillatesalkylating reactants are described. The composition of these reactantsis a distinctive feature of the present invention.

Cracked Distillate Feeds

It was disclosed in the specification that the key factor in producingthe highly olefinic reactant feed of the present invention is hightemperature thermal cracking. Another factor is the origin and priortreatment of the petroleum residua to be cracked. The presence of themajor 1-n-olefin components of the cracked distillates depends on thepresence of normal alkyl groups in the crude oil. These olefins areformed by the cracking and dehydrogenation of n-alkyl aromatics andn-paraffins.

In the past the molecular structure of neither the petroleum residua northe thermally cracked distillates was known. Thus the desirablecharacteristics of the present distillate feeds were not recognized. Animportant step in the present invention was the structural analysis ofthe complex distillate feeds by high resolution capillary gaschromatography (GC) magnetic resonance spectroscopy (NMR) and combinedcapillary gas chromatography/mass spectrometry (GC/MS).

The distillate fractions used as feed in the present invention werederived by the Fluid-coking of vacuum residua produced from NorthwestAmerican crude. Other distillate feeds, derived from Arabian crude in aFlexicoking unit, had similar compositions. The composition of thesefeeds in a wide carbon range is described in U.S. patent applicationSer. No. 914,802, filed on Oct. 4, 1986 and now allowed. Thisapplication is incorporated by reference.

The composition of the C₄ to C₁₂ coker naphtha distillate was analyzedby GC using a temperature programmed 50 m column. The key components ofthe mixture were identified by GC/MS, with the help of standards asrequired. The gas chromatogram obtained is shown in FIG. 1 with symbolsindicating the 1-n-olefin and n-paraffin components of various amounts.In the C₆ to C₁₂ range the 1-n-olefin to n-paraffin ratios range fromabout 1.1 to 2.1. The 1-n-olefins are the largest single type ofcompounds.

Lower cracking temperatures result in decreased olefin/paraffin ratios.For example, delayed coking which is carried out at a lower temperaturethan fluid coking gives distillates of lower ratios. An analysis of anaphtha fraction from a delayed coker gave an average of 0.31-n-olefin/n-paraffin ratio.

The broad C₃ to C₁₂ coker naphtha fraction was fractionally distilled,using a column equivalent to 15 theoretical plates with reflux ratio of10, to produce distillates rich in olefins and paraffins of a particularcarbon number. Selected fractions were studied by proton NMR using aJEOL GX 400 MHz spectrometer. FIG. 2 shows the NMR spectrum of theolefinic region of the naphtha with an indication of the chemical shiftregions assigned to the vinylic protons of various types of olefins. Aquantitative determination of the olefinic protons of the various typesof olefins was used to estimate olefin linearity. The relative molepercentages of olefins of varying carbon numbers were calculated on thebasis of amounts of the different types of olefinic protons. The resultsof these calculations and the boiling ranges of the fractions are shownin Table I.

The data of Table I show that the Type I olefins, i.e., monosubstitutedethylenes, are the major type of olefins in all the distillate fractionsas well as in the starting C₄ -C₁₂ naphtha. The percentage of Type Iolefins in the distillation residue is, however, reduced to less thanhalf of the original. It is assumed that this result is due to1-n-olefin conversion during the high temperature distillation. Minorvariations, between 32 and 50%, are also observed in Type I olefincontent of distillate cuts.

The second largest olefin type present in the naphtha and its distillateconsists of 1,2-disubstituted ethylenes. The percentage of these Type IIolefins varies between 18 and 26%. Most, if not all, of these olefinsare linear internal olefins.

Type III olefins, i.e., 1,1-disubstituted ethylenes were found to bepresent in amounts ranging from 12 to 17%. The major olefins of thistype were 2-methyl substituted terminal olefins. Their branching occursmostly at the vinylic carbon.

Type IV olefin, i.e., trisubstituted ethylenes, were the smallestmonoolefin components of these distillates. Their relative molarconcentration is in the 6 to 12% range.

Type V olefins, i.e., tetrasubstituted ethylenes, could not bedetermined by proton NMR.

Finally, Table I also lists small but significant quantities (8-16%) ofconjugated diolefins. The amounts listed for these olefins areapproximate because conjugated olefins may have a different number ofvinylic hydrogens per molecule dependent on the site of conjugation andthe presence of branching at vinylic sites.

The NMR spectra of naphtha fractions were also analyzed in the area ofaromatic and paraffinic protons to estimate the amounts of olefins. Fromthe percentage distribution of various types of hydrogens and theelemental analyses of these fractions, the weight percentage of varioustypes of compounds was estimated.

The type I olefins, mostly 1-n-olefins were estimated to be present inthese fractions in the range of 18.7 to 28.3%. These percentages dependon both the carbon number and the particular usually narrow boilingrange of the olefinic fractions studied.

                                      TABLE I                                     __________________________________________________________________________    Relative Amounts of Various Types of Olefins in Fluid Coker Naphtha           Determined by 400 MHz Proton Magnetic Resonance Spectroscopy                  Naphtha Carbon No.                                                                          Mole Percentage Distribution of Various Types of Olefins        Boiling Point, °F.                                                                   C.sub.4 -C.sub.12                                                                 C.sub.5                                                                          C.sub.6                                                                          C.sub.7                                                                          C.sub.8                                                                          C.sub.8                                                                          C.sub.9                                                                          C.sub.10                                                                         C.sub.11                                                                         C.sub.12                                                                         Residue                          Initial:      --- 80-                                                                              140-                                                                             195                                                                              245-                                                                             254-                                                                             293-                                                                             335-                                                                             374-                                                                             410-                                                                             425-                             Final:        410 100                                                                              150                                                                              205                                                                              257                                                                              262                                                                              30 359                                                                              390                                                                              425                                                                              --                               __________________________________________________________________________    Olefin                                                                            I: --CH═CH.sub.2                                                                    37  31 50 42 36 32 44 43 39 36 16                                   II:                                                                              --CH═CH--                                                                        20  25 18 25 26 26 22 22 23 28 28                                   III:                                                                             --C═CH.sub.2                                                                     17  13 15 14 22 22 14 14 12 11 15                                   IV:                                                                              --C═CH--                                                                         12  22 10  8  6 07 08 12 10 11 21                                Conjugated Diolefin.sup.a                                                                  14  10  8 11 11 13 12 15 16 14 20                               __________________________________________________________________________     .sup.a The conjugated diene values are only approximate.                 

In the C₆ to C₁₀ range these values for the Type I olefins approximatelycorrespond to the values obtained for 1-n-olefin by GC.

The total olefin content of these fractions is in the 47 to 62% range asdetermined by NMR. It is noted that the conjugated diolefins areincluded in this percentage since they are converted to monoolefinsunder hydroformylation conditions or by a prior mild hydrogenation. Dueto differences in the boiling points of olefin isomers, the relativeproportion of linear versus branched olefin components is of coursesomewhat dependent on the boiling range of the feed. The table alsoshows significant and increasing amounts, up to 25%, of aromaticcomponents in the various naphtha fractions. The aromatics are mostlyhydrocarbons, i.e. alkylbenzenes and naphthalenes, but also containsignificant amounts of alkylthiophenes and benzothiophenes. In thehigher carbon fractions most of the sulfur is in the form of theseheteroaromatic compounds.

Table II shows the elemental composition of Billings Fluid-coker naphthafractions. Most importantly, the data of the table indicate a highpercentage of sulfur. Surprisingly, in the C₈ and higher fractions,little of this sulfur is in the form of mercaptans. According to GC/MS,most of the sulfur of the C₈ to C₁₂ fractions is in the form ofalkylthiophenes.

In the present examples, the C₈ and C₉ fractions of Billings Fluid-cokernaphtha were used as alkylating feed. The C₄ to C₁₂ naphtha and C₉ toC₁₆ light gas oil fractions overlap. A C₁₂ fraction of BillingsFluid-coker light gas oil was also employed in an example.

Similar characterizations were performed on a light coker gas oilproduced by the same Fluid-coking unit from which the coker naphtha wastaken.

FIG. 3 shows the capillary GC of the light gas oil in the C₉ to C₁₆range. About 90% of the components are in the C₁₀ to C₁₅ carbon range.The C₁₁ to C₁₃ components are particularly large. Obviously, there issome overlap between this composition and that of the broad cut naphtha.

As it is indicated by the symbols of the figure, the main components arethe 1-n-olefins and the n-paraffins. In general, the concentrations ofthe 1-n-olefins are greater than those of the corresponding paraffins.The 1-n-olefin to n-paraffin ratio is apparently maintained withincreasing carbon numbers.

The light gas oil fraction was fractionally distilled to produce narrowcut distillates of a particular carbon number.

                                      TABLE II                                    __________________________________________________________________________    Elemental Analyses of Distillate Fractions of Fluid Coker Naphtha                           Carbon Hydrogen Sulfur and Nitrogen Content of Naphtha and                    its Fractions                                                   Naphtha Carbon Number                                                                       C.sub.4 -C.sub.12                                                                 C.sub.5                                                                          C.sub.6                                                                          C.sub.7                                                                          C.sub.8                                                                          C.sub.9                                                                          C.sub.10                                                                         C.sub.11                                                                          C.sub.12                                                                          Residue                           Boiling Point, °F.:                                                             Initial                                                                            --- 80-                                                                              140-                                                                             195-                                                                             245-                                                                             290-                                                                             335-                                                                             374-                                                                              410-                                                                              425-                                       Final                                                                              410 100                                                                              150                                                                              205                                                                              257                                                                              300                                                                              350                                                                              390 425 --                                __________________________________________________________________________    Carbon, %            85.64                                                                            85.81                                                                            85.83                                                                            86.10                                                                            86.41                                                                            86.11                                                                             85.98                                                                             85.23                             Hydrogen, %          14.39                                                                            14.01                                                                            13.49                                                                            13.18                                                                            12.95                                                                            12.39                                                                             12.33                                                                             10.75                             Mercaptan Sulfur (SH), ppm                                                                   600                                                                              1770                                                                              850                                                                              450                                                                              80                                                                               20                                                                               60                                                                               30  100                                                                               490                              Total Sulfur, ppm                                                                           8900                                                                              1700                                                                             1300                                                                             2200                                                                             5100                                                                             5900                                                                             8800                                                                             12,000                                                                            13200                                                                             --                                Total Nitrogen, ppm                                                                          159                                                                               141                                                                              46                                                                               25                                                                               45                                                                               158                                                                              134                                                                             135  136                                                                              1022                              % SH (100 SH/Total)                                                                         6.74                                                                               100                                                                             65.38                                                                            20.45                                                                            1.57                                                                             0.34                                                                             0.68                                                                             0.25                                                                              0.76                                  Total Sulfur Compounds, %                                                                       0.40                                                                             0.36                                                                             0.71                                                                             1.86                                                                             2.42                                                                             3.99                                                                             5.96                                                                              7.14                                  __________________________________________________________________________     *The percentages of sulfur compounds in the various distillate fractions      were calculated, assuming that they contain 2 carbon less per molecule        than the hydrocarbon compounds of they fraction of a certain carbon           number.                                                                  

The light gas oil and these fractions were also studied by proton NMR. Aquantitative analysis showed that this gas oil is highly olefinic with astrong aliphatic character in that 88.2% of the hydrogens in the mixtureare on saturated carbons, 6.2% on olefinically unsaturated carbons andonly 5.6% on aromatic rings.

Selected distillate cuts of the light gas oil were also analyzed by NMRin a similar manner. The distribution of their vinylic hydrogens wasparticularly studied to determine the relative amounts of the varioustypes of olefins present. The results are summarized in Table III.

The data of Table III show that the relative olefin percentages of thedistillate cuts vary. However, the percentage of the Type I olefins,including the desired 1-n-olefins, is generally more than a third of thetotal. The type I and II olefins combined, which includes all the linearolefins represent more than 55% of the total. The vinylically branchedolefins are present in less than 35% amounts. The percentages of theconjugated diolefins are included in the table since they are convertedto monoolefins during hydroformylation. However, the diene structuresare uncertain and as such of approximate values.

Type III also shows the distribution of olefin types in case of fournarrow cut C₁₂ distillate fractions. As expected varying amounts of thedifferent types of olefins of different boiling points were found to bepresent. Thus the proportion of the Type I olefins changed from 45.5 to33.8%.

From the distributions of various types of olefinic hydrogens, theweight percentages of the various types of olefins were estimated. Theestimate of total olefins including dienes is between 50.4 and 61.7%. Itis noted that the 61.7% value is for the C₁₆ fraction which wasdistilled with decomposition. As a result of cracking this fractioncontained not only C₁₆ but lower molecular weight olefins as well. Inthe case of the C₁₂ range, four narrow cut fractions were analyzed todetermine changes in the proportion of different types of compounds.Only moderate changers were found in total olefin concentration (45.5 to54.4%).

To illustrate the detailed composition of the present gas oil feeds andto show the effect of polar adsorbents on separations, more detaileddata are provided on a narrow C₁₂ fraction on the basis of GC/MSanalyses. Such a cut cannot be separated on a nonpolar (boiling point)methylsilicone GC column. However, it was found that a highly polar typeCP Sil 88 column (with a cyanopropylated silicone stationary phase)separated the various types of components according to their polarity.

                                      TABLE III                                   __________________________________________________________________________    Relative Amounts of Various Types of Olefins in Light Fluid Coker Gas         Oil                                                                           Determined by 400 mHz Proton Magnetic Resonance Spectroscopy                              Olefin Type in Gas Oil Fraction, %                                Gas Oil Carbon Number                                                                     C.sub.9 -C.sub.16                                                                 C.sub.9                                                                          C.sub.11                                                                         C.sub.12                                                                         C.sub.13                                                                         C.sub.14                                                                         C.sub.15                                                                         C.sub.16                                                                         Narrow C.sub.12 Cuts                     __________________________________________________________________________    Boiling Point, °F. Initial                                                         293 335                                                                              365                                                                              405                                                                              442                                                                              475                                                                              505                                                                              525                                                                              405                                                                              412                                                                              415                                                                              423                             Calcd. for 1 Atm. Final                                                                   307 345                                                                              385                                                                              425                                                                              454                                                                              485                                                                              522                                                                              535                                                                              412                                                                              415                                                                              423                                                                              425                             Olefin I: CHCH.sub.2                                                                      42  37.1                                                                             43.6                                                                             40.0                                                                             38.5                                                                             43.5                                                                             44.0                                                                             37.9                                                                             43.4                                                                             45.5                                                                             42.5                                                                             33.8                            II: CHCH    22  16.4                                                                             16.8                                                                             22.0                                                                             17.3                                                                             21.2                                                                             21.6                                                                             16.2                                                                             19.6                                                                             17.5                                                                             20.3                                                                             23.4                             ##STR30##  16  16.4                                                                             12.3                                                                             13.4                                                                             18.7                                                                             16.1                                                                             12.2                                                                             18.6                                                                             15.6                                                                             12.3                                                                             12.0                                                                             14.5                             ##STR31##   7  18.3                                                                             15.9                                                                             12.7                                                                             15.5                                                                              9.1                                                                             13.1                                                                             15.9                                                                              9.5                                                                             14.7                                                                             14.0                                                                             15.1                            Conjugated Diolefins                                                                      14  11.8                                                                             11.3                                                                             11.9                                                                             10.1                                                                             10.1                                                                              9.1                                                                             11.3                                                                             11.9                                                                              9.9                                                                             11.2                                                                             13.2                            __________________________________________________________________________

[This column is particularly suitable for the analysis of high boilingfractions since it has a high use temperature limit (about 275° C.)].These components could then be largely identified via GC/MS studies. Twocapillary GC traces with the groups of components identified are shownby FIG. 4.

The effluent of the above polar capillary column was split and led to aflame ionization and a sulfur specific detector. The chromatogram of theflame ionization detector shows the distribution of the organiccompounds according to polarity in the lower part of the Figure. Theupper chromatogram produced by the sulfur specific detector shows theelution of the sulfur compounds in the order of their polarity.

The lower GC of FIG. 6 shows good separation of the aliphatic,monoaromatic and diaromatic hydrocarbon components of the C₁₂ fraction.With the help of GC/MS the aliphatic components could be broken down toparaffins, olefins plus diolefins. Their percentages were 18.6 and50.5%, respectively. The monoaromatics included alkylbenzenes,naphthenobenzenes and trace amounts of alkylthiophenes. The total amountof monoaromatics was 28.2%. The main diaromatic compounds were indene,nephthalene and benzothiophene.

The upper, sulfur specific GC of FIG. 4 shows that essentially all thesulfur compounds of the C₁₂ fraction were aromatic. The majority werealkyl thiophenes. Benzothiophene was also present in significantamounts.

A similar analysis of the C₁₄ fraction showed an even better separationof the components according to their polarity. In this case thedistribution of the aliphatic components was similar but the majoraromatic components were dinuclear: methylnaphthalenes andmethylbenzothiophenes.

The distillate fractions of light gas oil were also analyzed forelemental composition, particularly for sulfur and nitrogen compoundsand mercaptans. The data obtained are summarized in Table IV.

The percentages of carbon and hydrogen were rather well maintained withincreasing molecular weights. They indicate that the aliphatic characterof the gas oil was fairly maintained. The total sulfur content remainedat about 1% in the C₉ to C₁₂ range. Thereafter, there was a rapidincrease of sulfur up to 2.82% in the C₁₆ fraction. It is noted thatthere was increasing decomposition during the distillation of thesefractions. When the C₁₆ fraction was redistilled a broad molecularweight range of 1-n-olefins was found in the distillates.

                                      TABLE IV                                    __________________________________________________________________________    Elemental Composition of Light Fluid Coker Gas Oil                            Gas Oil Carbon Number                                                                       C.sub.9                                                                          C.sub.10                                                                         C.sub.11                                                                         C.sub.12       C.sub.13                                                                         C.sub.14                                                                         C.sub.15                                                                         C.sub.16                       Boiling Point, °F.                                                               Initial                                                                           293                                                                              335                                                                              365                                                                              405                                                                              405                                                                              412                                                                              415                                                                              423                                                                              442                                                                              475                                                                              505                                                                              525                            (Calcd. for 1 Atm)                                                                      Final                                                                             307                                                                              345                                                                              385                                                                              425                                                                              412                                                                              415                                                                              423                                                                              425                                                                              454                                                                              485                                                                              522                                                                              535                            __________________________________________________________________________    Carbon, %     86.10                                                                            85.62                                                                            85.77                                                                            86.17                                                                            85.71                                                                            85.11                                                                            85.48                                                                            86.14                                                                            85.74                                                                            85.65                                                                            84.51                                                                            84.77                          Hydrogen, %   12.58                                                                            12.40                                                                            12.81                                                                            12.29                                                                            11.79                                                                            12.47                                                                            12.47                                                                            12.89                                                                            11.92                                                                            11.69                                                                            11.69                                                                            12.22                          Total Sulfur, %                                                                             1.06                                                                             1.06                                                                             1.01                                                                             1.15                                                                             1.39                                                                             1.14                                                                             0.96                                                                             0.97                                                                             1.56                                                                             2.34                                                                             2.62                                                                             2.82                           Total Nitrogen, %                                                                           .0163                                                                            .0244                                                                            .0243                                                                            0.131                                                                            .0294                                                                            .0364                                                                            .0352                                                                            .0289                                                                            .0395                                                                            .0306                                                                            .0652                                                                            .0713                          Mercaptan Sulfur, %                                                                         .0084 0.105                                                                            .0118                                                                            .0132                                                                            .0115                                                                            .0116                                                                            .0127                                                                            .0061                                                                            .0084                                                                            .0825                                                                            0.1395                         Sulfur Compounds, %.sup.a                                                                   4.17                                                                             4.63                                                                             4.86                                                                             5.53                                                                             6.69                                                                             5.49                                                                             4.62                                                                             4.68                                                                             7.50                                                                             12.28                                                                            14.90                                                                            17.27                          __________________________________________________________________________     The weight percentages of sulfur compounds were calculated on the basis o     total sulfur found assuming that the sulfur compounds were C.sub.3 to         C.sub.5 alkylthiophenes in the C.sub.9 to C.sub.11 olefin range,              benzothiophene in the C.sub.12 -C.sub.13 range, C.sub.1 to C.sub.13           benzothiophenes in the C.sub.14 to C.sub.16 range                        

This suggests the breakdown of nonvolatile aliphatic sulfur compounds togenerate olefins and mercaptans.

The total nitrogen contents of the distillates were more than an orderless than that of the total sulfur. The mercaptan content is generallyeven lower. However, both the nitrogen and mercaptan contents rosesharply in the C₁₅ and C₁₆ fractions.

Separation of Olefinic Feed Components

It was found that fractions rich in paraffins and/or olefins andaromatic fractions can be separated from thermally cracked distillatesderived from petroleum residua. On cooling such distillates of high1-n-olefin and n-paraffin content, it was discovered that these majorcomponents cocrystallize and can thus be separated. The resultingα-olefin/paraffin mixtures can be either used as such in olefinreactions or further separated.

In a study of model compounds we established that suitable mixtures forthe present separation are those which contain 1-n-olefins and paraffinshaving a range of carbon atoms. If the 1-n-olefin and n-paraffincomponents are in a single carbon fraction, they do not tend tococrystallize or to form any solid solution. Effective cocrystallizationof a n-paraffin of a certain carbon numbers occurs with a 1-n-olefinhaving two more carbons per molecule. Thus we found that eicosane (C₂₀°) cocrystallized with docosene (C₂₂ ⁼) while eicosane and eicosene didnot.

Experiments with a C₉ -C₁₉ fraction of Fluid-coker gas oil demonstratedthat the 1-n-olefin and n-paraffin components can be separated bycrystallization. This is indicated by FIG. 5 which shows the capillarygas chromatograms of this feed and the separated mixture. In theexperiment illustrated by this figure, a 5% methyl ethyl ketone (MEK)solution of the feed was cooled by dry ice and filtered and washed withcold MEK to separate the 1-n-olefin - n-paraffin (C_(n) ⁼ +C_(n) °)mixture. A toluene solution of the separated crystals was then analyzedby capillary GC.

FIG. 5 shows that the C_(n) ⁼ +C_(n) ° components represent about 41.3%of the feed while 93.4% of C_(n) ⁼ +C_(n) ° is present in thecrystalline mixture which was separated.

This method of separation could be realized with other, possibly moreadvantageous solvents. Olefin-paraffin mixtures could be obtained whichthen could be easily processed further to separate the olefins from theparaffins via molecular sieve (Parex process).

It was also found that Flexicoker and Fluid-coker distillates can 8eselectively extracted by polar solvents as sulfonates and acetonitrileto yield extracts highly enriched in aromatics including sulfurcompounds. The remaining raffinate rich in paraffins and olefins is amuch improved feed of greatly reduced sulfur content. n-Paraffin andn-olefin rich feeds can be similarly separated by adsorption e.g. byusing zeolites. This finding is illustrated by the following tabulationshowing the results of single stage extraction with sulfolane at 20° C.

    ______________________________________                                                 Composition by GC                                                                           Raffinate                                                                              Extract                                       Components Feed        ˜90%                                                                             ˜10%                                    ______________________________________                                        Paraffins  26          29        6                                            Olefins    64          66       49                                            Aromatics  10           5       39                                            ______________________________________                                    

The olefin rich fractions resulting from these separations and otherssuch as adsorption can be used for the alkylation of phenol, olefins,aromatic hydrocarbons and the like. The aromatic components can bereacted with coker distillate olefins of choice of further purified andthen utilized.

The present invention is further described in the following illustrativeexamples which, however, are not presented for the purpose of limitingthe scope of the invention, but for the purposes of illustrating severalembodiments thereof.

EXAMPLE 1

This example illustrates the alkylation of excess phenol with a C₁₂olefin containing a fraction of Fluid-coker gas oil from a thermalcracking process.

A stirred mixture of 1035.2 g (11 mole, 100% excess) phenol and 1851.5 gof a C₁₂ distillate fraction of a fluid coker gas oil containing about50% isomeric dodecenes (928 g, 5.5 moles) in a 5 liter flask was heatedby a heating bath under nitrogen to 110° C. At that temperature, 419.9 gof a dry crosslinked polystyrene sulfonic acid sold under the tradenameAmberlyst 15 by the Rohm and Haas Co. (equivalent to 1.97 mole sulfonicacid) was added. An immediate exothermic reaction occurred which raisedthe temperature of the mixture to 130° C. within 2 minutes. At thatpoint the mixture was cooled to about 115° C. and kept at thattemperature for 4 hours. Periodic analyses of the mixture by packedcolumn chromatography indicated the following percentages ofmonododecylphenol and didodecylphenol:

    ______________________________________                                                     Dodecylphenol Products, %                                        Reaction Time Hrs.                                                                           Mono-      Di-                                                 ______________________________________                                        1              35.6       7.1                                                 2              39.6       7.7                                                 4              44.4       7.8                                                 ______________________________________                                    

These data indicate that most of the reaction took place within thefirst hour. Due to the excess phenol employed, the ratio of mono-vs.didodecylphenol products did not increase significantly with increasingdodecene conversion. At the end of the four hour reaction period thesetwo products together were present in 52.2% concentration. The finalweight ratios of the mono- vs. didodecylphenol were 85 to 15. On thebasis of the GC data 1282 g of monododecylphenol was formed which is 88%of the calculated yield.

The final reaction mixture was filtered with suction using a glassfilter of medium frit to remove the catalyst. The catalyst was thenwashed with toluene and the filtrates were combined and fractionallydistilled in vacuo to separate the products and unreacted feedcomponents. The monododecylphenol product was obtained at between 122°and 145° C. at 0.05 mm. The didodecylphenol was distilled between 192°C. and 200° C. at 0.05 mm. Elemental analysis was obtained. Formonododecylphenol, C₁₈ H₃₀ O: Calcd. C, 82.38%; H, 11.52% found C,82.69%; H, 10.64%; S, 0.25%. For didodecylphenol, C₃₀ H₅₄ O: Calcd. C,83.65%; H, 12.64%. Found C, 83.90%; H, 10.39%.

The structures of the mono- and di-dodecylphenol products were alsosubjected to a ¹³ C NMR study. The monododecylphenol was determined tohave 36.5% of the ortho-substituted isomer and 63.5% of theparasubstituted phenol. In the case of dodecylphenol obtained by thereaction of isododecene with phenol, the ortho isomer is much lessgenerally in the range of 4% to 10%. The branchiness of the presentsemilinear monododecylphenol product was also compared with that of thehighly branched isododecylphenol on the basis of the number of methylgroups present per phenyl group. That number of methyl groups is two fora linear 1-n-dodecene derivative. Monobranched dodecenes lead toproducts having three methyl groups. Dibranched olefins provide productshaving four methyl groups. The degree of branchiness of these threeproducts is defined as 0, 1 and 2. The NMR study of the presentsemilinear monododecylphenol showed 2.9 mole methyl groups per moleculeand thus a branchiness degree of 0.9. In contrast, the commercialisododecylphenol had 4.9 methyls and thus a branchiness of 2.9. Due tothe NMR uncertainty of CH₂ versus CH₃ group assignments these values maynot be absolutely right but certainly indicate the much reducedbranchiness of the novel product.

The results of the comparative NMR studies of semilinear and highlybranched alkylphenols are shown by Table V. The data indicate majordifferences between the semilinear and branched isomers ofdodecylphenols and nonylphenols both with regard to the percentages ofortho - ortho isomers and the methyl branching number.

The above comparative data on the ortho to para isomer ratios and thedegrees of branchiness of the semilinear and branched nonylphenols arequalitatively displayed by their ¹³ C NMR spectra in FIG. 6. In thearomatic carbon region of 100 to 160 ppm, the figure shows that thesemilinear product has more o-substituted carbons (C--C o in the 132 to136 ppm range) than the highly branched. The less branched character ofthe semilinear product is indicated by the aliphatic region of thespectra, between 0 to 60 ppm. It is particularly apparent that thesemilinear product has fewer methyl groups in the 5 to 20 ppm region.

The composition of the starting C₁₂ light Fluid-coker gas oil fractionand the unreacted components of the same were compared by ¹ H NMRspectroscopy. Percentages of different types of hydrogens weredetermined. Based on the hydrogen distribution weight percentages of thevarious types of compounds were estimated as shown by Table VI.

The data show that out of the roughly 60% total olefins and conjugateddiolefins, about 59.3 reacted. Only about 0.7% of Type II, i.e. linearinternal, dodecenes were present in the recovered feed.

                  TABLE V                                                         ______________________________________                                        Comparison of Semilinear and Highly Branched Alkylphenols                     by .sup.13 NMR Spectroscopy                                                           Carbon %       Ortho   Methyl                                         Type of   Aro-    Ali-           Isomer                                                                              Branching                              Alkylphenol                                                                             matic   phatic  Methyl.sup.a                                                                         %     No.                                    ______________________________________                                        Semilinear                                                                              37.7    62.3    18.1   36.5  0.9                                    Dodecyl                                                                       Branched  33.2    66.8    26.8    5.9  2.9                                    Dodecyl                                                                       Semilinear                                                                              42.2    57.8    16.4   19.3  0.3                                    Nonyl                                                                         Branched  39.5    60.5    27.8    5.0  2.2                                    Nonyl                                                                         ______________________________________                                         .sup.a Methyl carbons are estimated based on the mole fraction of             saturated carbon peaks between 26 and 5 ppm, excluding the 22.5 ppm           methylene peak. The methyl carbons of tbutyl and neopentyl groups are not     included.                                                                

EXAMPLES 2 AND 3

This example, illustrates the alkylation of phenol with excess C₉ olefincontaining a fraction of Fluid-coker gas oil.

A stirred mixture of 591 g (6.28 moles) phenol and 2000 g of a C₉fraction in a fluid coker gas oil containing about 60% nonenes (1200 g,9.51 moles) in a 5 liter flask was heated by a heating bath to 110° C.At that temperature, 388.7 g of a sulfonic acid catalyst was added. Amild exotherm occured. The reaction mixture was kept at 115° C. for 4hours. The product formation in the reaction mixture was followed byperiodic chromatographic analysis and is shown by the followingtabulation.

    ______________________________________                                                      Nonylphenol Products, %                                         Reaction Time Hrs.                                                                            Mono-      Di-                                                ______________________________________                                        1               24.8       2.3                                                2               29.2       2.7                                                4               36.3       6.3                                                ______________________________________                                    

The final reaction mixture was filtered using a Buchner funnel withsuction. The Amberlyst 15 was washed twice with 400 ml n-hexane each anddried in vacuo. The resulting recovered catalyst weighted 462 g and thusshowed a 19% weight increase.

                                      TABLE VI                                    __________________________________________________________________________    Hydrogen and Compound Type Distribution in the Feed                           and Recovered Components of C.sub.12 Billings Fluid Coker Light Gas Oil                   Types of Monoolefins (Dodecenes)                                                                            Aromatics                           Sample                                                                              Dimension                                                                           I      II     III   IV    Conj.                                                                             Mono-                                                                              Naphtha                                                                            Par-                      Type  of Data                                                                             --CH═CH.sub.2                                                                    --CH═CH--                                                                        --C--CH.sub.2                                                                       --C═CH--                                                                        Dienes                                                                            Nuclear                                                                            lene affinic.sup.a             __________________________________________________________________________    Feed  % H   3.18   0.99   0.73  0.40  1.09                                                                              4.56 0.77 88.48                     Unreacted.sup.b                                                                     % H   0      0.24   0     0     0   29.50.sup.c                                                                        1.19 70.27                     Feed  % Wt  24.0   11.2   8.3   9.1   8.1 21.7 1.7  16.0                      Unreacted                                                                           % Wt  0      0.7    0     0     0   --   --   --                        __________________________________________________________________________     .sup.a Hydrogens on saturated carbons. Value includes alkyl hydrogens.        .sup.b The recovered unreacted feed contained 34% unreacted phenol.           .sup.c Includes phenol.                                                  

The recovered catalyst was used in Example 3 which was carried out inthe same manner. The results were also similar:

    ______________________________________                                        Reaction        Nonylphenol                                                   Time            Products, %                                                   Hrs.            Mono-   Di-                                                   ______________________________________                                        1               21.6    1.8                                                   2               28.0    4.0                                                   4               34.9    3.4                                                   ______________________________________                                    

The resulting reaction mixture was filtered and the catalyst was washedin the same manner, except that toluene was used for washing. The use oftoluene resulted in the recovery of a cleaner catalyst. The dried weightof the catalyst was 411 g, just 6% above the original.

The average percentage of monononylphenol in the above examples was35.6%. The average ratio of mono- versus dinonylphenol was 85 to 15. Onthe basis of the GC data the weight of the combined product is 1845 g.This corresponds to 66.7% of the calculated yield.

The combined filtrates and washings were fractionally distilled in vacuoto separate the uncoverted reactants and products. The unconverted C₁₂fraction was distilled at first about 40° C. at 1 mm. It was a colorlessliquid. This was followed by the unconverted phenol at about 60° C. at0.1 m. The product was distilled with minor decomposition, essentiallydealkylation, apparently due to the presence of residual acid catalyst.Thus some of the crude product distillates were combined and redistilledto provide a total of 1489 g (53.8%) of monononylphenol as an almostcolorless liquid boiling in the range of 105° and 120° at 0.05 mm. Thedinonylphenol by-product boiled between about 160° and 182° C. at 0.05mm. The amount of this viscous orange liquid distillate product was 204g.

Analysis was as follows: Mononoylphenol, C₁₅ H₂₄ O. Calcd. C, 81.76%; H,10.98%. Found C, 82.90%; H, 10.59%; S, 0.15%. Dinonylphenol, C₂₄ H₄₂ O.Calcd. C, 83.17%; H, 12.22%. Found: C, 83.41%; H, 10.38%; S, 0.58%.

A study of the distilled monononylphenol fraction by ¹³ C NMRspectroscopy indicated that the nonyl groups were more branched than thedodecyl groups of the product of Example 1. The increased branchiness ofthe alkyl groups in the present case is apparently the result of lowolefin conversion. (At low olefin conversion, only the more branchedolefin components of the cracked distillate react under selectivealkylation conditions). NMR also showed that the ratio ofortho-nonylphenol to para-nonylphenol was 19 to 81. This ortho/pararatio is less than half of that observed in the case of ortho andpara-dodecylphenols. Again, the lower ortho/para ratio is due to theincreased branching of the alkyl substituents.

The composition of the starting C₉ Fluid-coker naphtha fraction and therecovered unreacted components of the same were compared by ¹ H NMRspectroscopy. The results are shown by Table VII. The data of the tableindicate that the mono-olefin components, i.e., nonenes, were onlypartially converted to nonylphenols. Much of the Type I olefin,1-n-nonene, was isomerized to Type II olefins, internal olefins.However, only part of the latter reacted further to yield the desiredalkylphenol products.

Although the nonylphenol of the present example is of a more branchedcharacter than the analogous product of Example 1, it is neverthelessdistinctly different from the highly branched t-nonylphenols of theprior art. This has been determined by comparison of the ¹³ C NMRspectra of the product of this experiment and t-nonylphenol.

EXAMPLE 4

This example demonstrates the alkylation of phenol with a C₈ fraction ofa fluid coker naphtha containing equimolar amounts of octenes.

A magnetically stirred mixture of 1.2 g (12.75 mmole of phenol and 2.4 gof a C₈ distillate cut of a Fluid-coker naphtha containing 60% (1.43 g,12.75 mmole) of octenes and 0.54 g of catalyst that was used in the typeof Example 1 was heated in a closed vial at 90° C. for 8 hours. In asecond run, an identical reaction mixture was employed; however, thetemperature used was 115° C. In a third run, a C₈ coker naphtha wasreplaced by a 60/40 weight mixture of 1-octene and n-nonane. Thismixture was then reacted with phenol in the same manner at 115° C. toobtain the comparative data on its reactivity. The percentages of mono-and dioctyphenols formed in the three reaction mixtures wereperiodically determined by GC. The data obtained are shown in thefollowing.

                                      TABLE VII                                   __________________________________________________________________________    Hydrogen and Compound Type Distribution in the Feed and                       Recovered Components of C.sub.9 Billings Coker Naphtha                                    Types of Monoolefins (Nonenes)                                                                          Total                                   Sample                                                                              Dimension                                                                           I      II     III   IV    Mono-                                                                             Conj.                                                                             Arom-                                                                             Par-                        Type  of Data                                                                             --CH═CH.sub.2                                                                    --CH═CH--                                                                        --C═CH.sub.2                                                                    --C═CH--                                                                        Olefins                                                                           Dienes                                                                            atics.sup.c                                                                       affinic.sup.a               __________________________________________________________________________    Feed  % H   4.35   1.12   0.90  0.58  8.33                                                                              1.39                                                                              4.37                                                                              87.30.sup.a                                                 0.61                                          Unreacted.sup.b                                                                     % H   0.34   2.13   0           3.07                                                                              0   16.58                                                                             77.73.sup.a                 Feed  Wt %  25.2   9.8    7.8   10.1  52.9                                                                              7.9 14.2                                                                              24.9                                                        9.4       43.8                                Unreacted.sup.b                                                                     Wt %  1.7    16.4   0           27.5                                                                              0       27.7                        __________________________________________________________________________     .sup.a Hydrogens on saturated carbons. Value includes alkyl hydrogens.        .sup.b The recovered unreacted feed contained 34 wt % toluene.                .sup.c Includes toluene solvent.                                         

    ______________________________________                                        Mono- and Dioctylphenol Products, %                                           Reaction                                                                              Run 1       Run 2       Run 3                                         Time    Octenes, 90°                                                                       Octenes, 115°                                                                      1-Octene, 115°                         Hours   Mono-    Di-    Mono-  Di-  Mono-  Di-                                ______________________________________                                        1       13.8     0.4    33.7    2.9 28.59  2.3                                2       18.7     1.2    42.2    5.1 33.74  4.9                                4       25.3     1.5    36.37  16.2                                           8       32.8     2.3                                                          ______________________________________                                    

The results show that the alkylation of phenol in the presence ofAmberlyst 15 is much faster at 110° C. than at 90° C. At 115° C., thereaction with the C₈ cut of coker naphtha is essentially complete in 2hours. At comparable dilution, 1-n-octene is less reactive buteventually leads to more dialkylated phenol than the isomeric octenes ofcoker naphtha.

EXAMPLE 5

This example demonstrates the alkylation of phenol 130° C. with a C₉Fluid-coker naphtha containing a small excess of olefins.

Phenol was reacted with 10% excess of Fluid-coker nonenes at 130° C. inthe presence of 5 wt. % Amberlyst 15 in the manner described in Examples2 and 3. The data indicate that the conversion was substantiallycomplete in 4 hours. The ratio of mono-versus dinonylphenol products wasfound to be substantially similar to those of Examples 2 and 3 in spiteof the different ratios of reactants used.

The final reaction mixture was worked up to obtain mono- anddinonylphenol products via fractional distillation. The first distillatefractions containing the more branched nonylphenol isomers was obtainedbetween 94° and 104° C. at 0.05 mm. The latter distillate fractions withthe more linear nonylphenols were distilled between 104° and 119° C. at0.5 mm. Both sets of distillates were of similar amounts and found to besimilar in composition, thus confirming their isomeric character.

Elemental Analyses. Monononylphenol, C₁₅ H₂₄ O. Calcd: C, 81.76; H,10.98. Found for first distillate: C, 82.04; H, 10.10; S, 0.25. Foundfor second distillate, C, 82.50; H, 9.84; S, 0.15. Dinonylphenol, C₂₄H₄₂ O. Calcd: C, 83.17; H, 12,22. Found: C, 83.41; H, 10.01; S, 0.35.

EXAMPLE 6

This example demonstrates the alkylation of phenol with equimolar C₉olefin containing fraction of Fluid-coker naphtha, at 150° C.

A magnetically stirred mixture of 1.8 g (19 mmole) phenol, 4 g of a C₉distillate cut of Fluid-coker naphtha, containing 60%, i.e.. 2.4 g (19mmole) of nonenes, and 0.29 g (5 wt. %) Amberlyst (1.4 mmole sulfonicacid equivalent) was heated at 85° C. for 16 hours and then at 150° C.for 8 1/2 hours. During the reaction, samples of the liquid reactionmixture were periodically taken and analyzed for mono- and dinonylphenol. The data obtained are shown in the following.

    ______________________________________                                        Reaction Conditions                                                           Tempera-  Time                                                                ture      Period       Nonylphenols %                                         °C.                                                                              Hours        Mono-    Di-                                           ______________________________________                                         85       16           14.4                                                   150       +2           38.3     4.0                                                     4            42.5     4.5                                                     8            45.0     6.0                                           ______________________________________                                    

The results show that at 85° C. little reaction occurs while at 150° C.mono-octylphenol is formed rapidly and selectively.

EXAMPLES 7 TO 9

This example shows the effect of varying temperatures and reactantratios on the alkylation of phenol with an olefinic C₉ fraction ofFluid-coker naphtha.

Magnetically stirred mixtures of phenol and a C₉ distillate cut ofBillings Fluid Coker naphtha of 60% nonenes content were reacted in thepresence of 15% Amberlyst catalyst in the manner described in Example 6.Different reaction temperatures and phenol to nonenes reactant ratioswere used. The mixtures were periodically samples and analyzed by GC.The data obtained are shown by Table VIII.

Comparison of the data of Examples 6 and 7 indicates that the reactionis considerably faster at 130° than at 115° C. However, the reactionrate could be sufficiently increased at 115° C. by increasing the amountof catalyst used. Thus the rate at 115° C. in the presence of 15%Amberlyst in Example 8 was found to be similar to that obtained at 130°C. in the presence of 5% Amberlyst in Example 4.

                  TABLE VIII                                                      ______________________________________                                        Effect of Reactant Ratios on Phenol                                           Alkylation with C.sub.9 Fluid-coker Naphtha                                               Reaction Conditions                                                       Phenol to Tempera-  Time   Nonylphenols                               Example Nonenes   ture      Period in Mixture %                               No.     Ratio     °C.                                                                              Hours  Mono- Di-                                  ______________________________________                                        7       0.90      130       1      38.3  6.3                                                              2      49.4  9.5                                                              4      48.3  12.1                                                             8      51.9  20.3                                 8       0.90      115       1      22.0  4.7                                                              2      30.3  4.8                                                              4      36.8  6.3                                                              8      40.2  8.3                                  9       0.66      115       1      19.8  2.9                                                              2      29.2  5.6                                                              4      30    9.2                                  9       0.50      115       1      12.5  2.7                                                              4      25.7  8.6                                  ______________________________________                                    

A decreasing phenol to olefin ratio from 0.9 to 0.5 in Examples 7 to 9resulted in decreased product formation. It is apparently advantageousto employ phenol in excess of the amount reacted to increase thereaction rate and selectivity.

EXAMPLE 10

This example shows a model compound study of phenol alkylation with1-octene in the presence of benzothiophene.

In a magnetically stirred, closed vial, a mixture of equimolar amountsof phenol and benzothiophene [0.94 g, (10 mmole) phenol and 1.34 g (10mmole) benzothiophene] and an equivalent amount of 1-octene (1.12 g, 10mmole) was reacted in the presence of 0.17 g Amberlyst 15 (5 wt %) at80° C. overnight. GC analyses of the reaction mixture by packed columnand capillary GC indicated that the octene selectively alkylated thephenol. According to packed column GC, the reaction mixture contained16% monooctylphenols and 1% monooctylbenzothiophenes. No significantamounts of either dioctylphenols or dioctylbenzothiophenes were formed.Capillary GC indicated an extensive isomerization of the starting1-octene reactant. Only 11.2% of the total octenes in the reactionmixture was 1-octene. o-Octyl-phenols and p-octylphenols constitutedabout 83% of the octylphenols. The remaining 17% were assumed to bem-octylphenols. In the case of both o-octylphenols and p-octylphenolsthe 2-methylheptylphenols were the main isomers. They were about 70% ofthe total. On further heating of the mixture dioctylphenols were formed,mostly via the further alkylation of o-octylphenols. Thus the resultingmixture consisted mostly of p-octylphenols and o, p-dioctylphenols;o-octylphenols were absent.

The results of phenol alkylation by 1-octene alone at 115° C. werequalitatively similar. The most apparent difference was the increasedisomerization of 1-octene and reduced percentages, about 55%, of the2-methyl-heptylphenol isomers compared to the other isooctylphenols.Overall, the study confirms the selective course of phenol alkylation byFluid coker olefins.

Procedure for the Alkoxylation of Semilinear Alkylphenols (EXAMPLES 11TO 15)

The ethoxylation and propoxylation of alkylphenols, derived from Fluidcoker distillates in previous examples, were mostly carried out inpressure tubes of about 9 ml capacity. These tubes were equipped with aTeflon screw valve and fit for use in a JEOL FX90Q multinuclear NMRspectrometer. Usually about 3 g of a reaction mixture was employed.

In a typical procedure, the alkylphenol and the catalyst and anonvolatile solvent, typically mesitylene, were added to the pressuretube. If sodium was used as a catalyst precursor, it was dissolved inthe alkylphenol to form sodium alkyphenolate prior to being added intothe tube. The last component to be added was ethylene oxide or propyleneoxide. Appropriate molar amounts of ethylene oxide were condensed to theother components into the evacuated tube which was then closed. Theliquid propylene oxide reactant was simply added to the mixture. Theclosed tubes containing the reaction mixtures were then heated in bathsat the desired reaction temperature. At the start of the heating themixture was shaken by hand to assure homogeneity. During the reaction,samples were periodically taken from the tubes, after cooling, for GCanalyses to determine the progress of the reaction.

In most of the alkoxylations, a monononylphenol product of Example 5 wasused as a starting reactant. This reactant was an early distillatefraction and as such contained 0.25% sulfur in the form ofalkylthiophenes. The latter, of course, do not react with epoxides.However, they tend to polymerize in the presence of strong acids.

EXAMPLE 11

This example illustrates the ethoxylation of semilinear nonylphenol.

Into each of four pressure tubes was placed 2.2 g (10 mmole) nonylphenolprepared in accordance with the process of this invention and 2.2 gmesitylene solvent. Five percent of the nonylphenol was present assodium nonylphenolate derived by the reaction of 0.012 g (0.5 mmole)sodium with the phenol. Thereafter, varying amounts of ethylene oxidewere condensed into the tubes; 15, 20, 30 and 100 mmoles, respectively.This resulted in ethylene oxide to nonylphenol reactant ratios of 1.3,2, 3 and 10.

The tubes were sealed and heated at 140° C. The first three mixtureswere kept at that temperature for 1 hour, the last for 15 minutes.Thereafter they were analyzed by packed column GC. The GC data indicateda complete reaction of ethylene oxide with the exception of the 15minute sample. The nonylphenol reactant was substantially converted ineach case. However, the impurities in the nonylphenol, apparentlynonylthiophenes of shorter retention times, did not react.

GC indicated the formation of ethoxylated nonylphenol products. Theratios of the variously ethoxylated nonylphenols were different, clearlydependent on the ethylene oxide to nonylphenol reactant ratios. Theresults are shown by Table IX.

                  TABLE IX                                                        ______________________________________                                        Effect of Reactant Ratios on the Degree of Ethoxylation                       of Semilinear Nonylphenol                                                     No. of                                                                        Ethoxy                                                                        Units  Distribution of Various Ethoxylated Products, GC%                      Per Mole                                                                             (At Varying Ethylene Oxide Nonylphenol Ratio)                          Product                                                                              (1.3)     (2)        (3)     (10)                                      ______________________________________                                        1      50.3      18.1       7.2     11.2                                      2      49.7.sup.b                                                                              76.1       38.5    16.2                                      3                5.8.sup.b  54.3.sup.b                                                                            32.4                                      4                                   40.2.sup.b                                ______________________________________                                         .sup.a The mixture of 10/1 ethylene oxide to nonylphenol was reacted for      only 15 minutes.                                                              .sup.b This percentage includes the species of higher ethoxylation as         well.   Due to the complexity of the Fluid-coker nonenes feed, a high         number of isomeric compounds was formed. Thus the distinction between     compounds of varying ethoxylation degrees was difficult and somewhat     arbitrary. However, comparatively valid distribution data were obtained     since the same assumptions were made in evaluating all the reaction     mixtures.

At the low ethylene oxide to nonylphenol ratio of 1.3, only mono-anddiethoxylated products were formed. At the oxide to phenol ratio of 3most of the products had 2 or 3 ethoxy units per molecule. In contrast,at an oxide to phenol ratio of 10 a broad distribution of ethoxylatedproducts was obtained. The degree of ethoxylation extended far beyondfour, even though not all the ethylene oxide reacted in the short, 15minutes, reaction time.

EXAMPLE 12

This example illustrates the propoxylation of semilinear nonylphenol.

The nonylphenols derived in accordance with the present inventionreacted with varying amounts of propylene oxide in a manner analogous toExample 11 above. These reactions were carried out in the presence of 5mole % sodium as catalyst precursor. Propylene oxide to nonylphenolreactant ratios of 1, 2 and 10 were used. The reaction mixtures wereheated at 140° C. and periodically sampled for GC analyses. At the 1/1and 3/1 oxide to phenol reactant ratios, selective propylene oxide ringopening by the phenol took place. On the basis of GC composition, therelative amounts of variously propoxylated nonylphenols were calculated.The data are shown in Table X.

                  TABLE X                                                         ______________________________________                                        Effect of Reactant Ratios on the Degree of Propoxylation                      of Semilinear Nonylphenol                                                     No. of Distribution of Various Propoxylated Products                          Propoxy                                                                              % by GC                                                                Units  Oxide to Phenol Ratio 1                                                                           Oxide/Phenol = 3                                   Per Mole                                                                             30 Min..sup.a                                                                           1 Hr..sup.a                                                                            3 Hrs. 1 Hr..sup.a                                                                          2 Hrs.                                ______________________________________                                        1      89.2      83.8     58.6   11.7   5.0                                   2      10.8      16.2     41.4.sup.b                                                                           39.7   39.5                                  3                                27.1   36.2                                  4                                21.5.sup.b                                                                           19.3.sup.b                            ______________________________________                                         .sup.a The reaction mixture contained unreacted propylene oxide.              .sup.b Includes species of higher propoxylation.                         

The data indicate that as the reaction progressed, the amounts of morehighly propoxylated species increased. At a nominally equimolar reactantratio (due to impurities in the phenol the real ratio was greater thanone) the main products were mono- and dipropoxylate. When a threefoldexcess of propylene oxide was used, the main products were di- andtripropoxylated nonylphenols. Beyond the tetrapropoxylated species,little product was formed.

In contrast to the above selective reactions at low propylene oxide tophenol ratio, propylene oxide polymerization became a major sidereaction when 10 moles of oxide were reacted with one mole of phenol at140° C.

EXAMPLE 13

This example compares the base and acid catalyzed ring opening reactionsof propylene oxide with monoethoxylated phenol as a model compound.

Monoethoxylated phenol was reacted with propylene oxide in the presenceof sodium as a catalyst precursor and 15 wt. % p-toluene sulfonic acidas a catalyst. The sodium was reacted with the monoethoxylated phenol toprovide 5 mole % sodium alcoholate as a catalyst. In both experiments,2.76 g (10 mmole) monoethoxylated phenol, 2.76 g mesitylene solvent and1.16 g (10 mmole) propylene oxide were employed. The reactions werecarried out in closed pressure tubes as usual at 140° C. for 1 hour.

In the presence of the base catalyst, propylene oxide conversion wascomplete and a highly selective ring opening reaction took place to formcompounds of the generic formula. ##STR32## GC analyses indicated thefollowing percentage distribution for the variously propoxylatedsecondary alcohol products: n=0: 9.6; n=1: 64.9; n=3: 18.2; n=4: 4.5;n=5: 2.8.

The acid catalyst was not soluble in the reaction mixture at roomtemperature but dissolved on heating. Acid catalysis was somewhat lesseffective and less selective than base catalysis. After one hour at 140°C., there was still 1% unconverted propylene oxide (6.5% of the originalamount) in the reaction mixture. Also, there was 5.77% propylene oxideoligomer present (equivalent to 37% of the propylene oxide reactantemployed) and 26.8% of monoethoxylated phenol. The major part of thepropylene oxide (57.2%) reacted with the monoethoxylated phenol to formprimary and secondary alcohols. The ratio of these alcohols for themonopropoxylated products according to capillary GC was the following:##STR33## These two compounds represent 75% of the propoxylatedproducts. The other 25% consists mostly of isomeric dipropoxylatedproducts.

EXAMPLES 14 AND 15

These examples describe the propoxylation of ethoxylated nonylphenols ofthis invention in the presence of base and acid catalysts.

As a reactant in these examples, an ethoxylated semilinear nonylphenolwas used. It contained almost equal quantities of the mono-anddiethoxylated nonylphenols in mesitylene solution. (As a catalyst 5 mole% the sodium alcoholate derivative was present.) The results wereanalogous to those observed with the model compounds in the previousexamples.

In the first example, 2.15 g of the above reactant was reacted with athreefold excess (0.75 g) of propylene oxide in a pressure tube. Onheating the reaction mixture at 140° C. for 1 hour, a base catalyzedreaction took place. GC analysis indicated that the ethoxylatedreactants were essentially all propoxylated. Most of the propylene oxideemployed (90%) was reacted selectively without any propylene oxideoligomer formation.

A comparative experiment (Example 15) was carried out in an identicalmanner, except for the acid catalyst. To the ethoxylated nonylphenolreactant (2.15 g), 0.37 g p-toluenesulfonic acid monohydrate was addedto neutralize the sodium alkoxide base and provide a 15% concentrationof the acid catalyst. Thereafter, a threefold molar excess of thepropylene oxide reactant (0.75 g) was added and the sealed mixture washeated at 140° C. for 1 hour. A subsequent GC analysis indicated thatpropoxylation occured but at a lower rate and less selectively than inthe case of the base catalyst.

EXAMPLE 16

This example illustrates the reaction of nonylphenol sodium compoundprepared in accordance with the present invention and n-octylphenolsodium with y-butanesultone.

For the first run, 2.2 g of a nonylphenol prepared in accordance withthis invention was reacted with 2.2 g of 25% methanolic sodiummethoxide, containing 10 mmoles of base. To the resulting sodiumnonylphenolate solution, 1.4 g (10 mmole) y-butanesultone was added toprovide a clear orange reaction mixture liquid. The reaction occurred onstanding at room temperatures. It was indicated by the precipitation ofcolorless 3-nonylphenylbutanesulfonic acid sodium crystals.Precipitation occurred overnight. About 0.4 g of the crystalline productwas isolated by filtration and drying. Its structure was confirmed byC¹³ NMR spectroscopy.

In the second run, a similar reaction was carried out with highly puren-octylphenol to determine the characteristic NMR parameters of its3-butane-sulfonate. These parameters were then used as diagnostic valuesin the confirmation of the structure of the nonyl derivative set forthabove.

A solution of n-octylphenol sodium was prepared using 0.67 g (3.2 mmole)n-octylphenol, 0.14 g (3.5 mmole) sodium hydroxide and about 3 g of a4/1 water/dioxane mixture with D₂ O locking solvent. To this reactantsolution 0.44 g (3.2 mmole) γ-butane-sultone was added and sulfonateformation was followed by ¹³ C NMR. NMR showed that the sulfonateconversion was complete on standing overnight. Reaction was alsoindicated by the formation of product crystals. The mixture was heatedat 70° C. to obtain a homogeneous solution and then a ¹³ C NMR spectrumwas taken at that temperature. The following characteristic chemicalshift values (ppm) were found for carbon fragments of the3-butanesulfonate group. ##STR34## Values in the above chemical shiftrange were also found for the analogous sulfonate product derived fromthe semilinear nonylphenol.

What is claimed is:
 1. A composition comprising of a mixture ofalkoxylated semilinear ortho and para alkylphenols of the formula##STR35## wherein R is a C₅ to C₃₅ alkyl group having an average of lessthan 2 branches and the ratio of ortho- to para isomers being in therange from about 10 ortho to 90 para to 40 ortho to 60 para;E isselected from the group consisting of CH₂ CH₂, CH(CH₃)CH₂ and CH₂CH(CH₃)_(n) is 1 to
 30. 2. The composition of claim 1 where R is nonyland E is CH₂ CH₂.
 3. Monoethoxylated semilinear nonylphenol according toclaim
 1. 4. An alkylation process comprising reacting an olefiniccracked petroleum distillate feed produced from petroleum residua byhigh temperature thermal cracking and containing 1-n-olefins as themajor type of olefin component and organic sulfur components inconcentrations exceeding 0.1% sulfur with phenol or cresol attemperatures between 20° and 450° C. in the liquid phase in the presenceof a strong acid catalyst in effective amounts to product alkylphenolsas the major products, and additionally reacting the alkylphenol productwith a reagent selected from the group consisting of ethylene oxide,propylene oxide, propanesultone, butanesultone, sulfur dichloride,formaldehyde, and phosphorus pentasulfide.
 5. The process of claim 4wherein the alkylphenol is reacted with ethylene oxide or propyleneoxide to produce an ethoxylated or propoxylated alkylphenol nonionicsurfactants.